Capillary active agents



Patented Feb .5 ,1946i 2,394,301

Winfrid Hentrich, Rodleben, near Dessau- Rosslau, and Heinz-JoachimEngelbrecht and Erik Schirm, Dessau, Germany; vested in the AlienProperty Custodian No Drawing. Application June 6, 1941,- Serial No.396,964. In Germany June 7, 1940' 3 Claims. (01. 260-400 This inventionrelates to capillary active agents and the process of making the same.

It. has been found that valuable capillary ac tive agents can beproduced by treating compounds havingthe general formula NHaALXNI-LYRwith acylating or alkylating agents containing at least three carbonatoms in the molecule. In this general formula -Ar denotes an aromatichydrocarbon residue which may also comprise core substituents such asfor instance halogen-, hydroxy1-, alky1-, alkoxy-residues or the like ora second amino-residue; prefierably Ar denotes a substitutedbenzol-resldue.

The residues X and Y denote either both the radical S02 or one of themthe radical S02 andthe other the radical CO.

R denotes an aliphatic or an aromatic hydrocarbon residue which may besubstituted.

For the production of the cap llary active agents there are preferablyused aminoaryl compounds following the general formula like.

matic residue of which contains groups capable of conversion into aminogroups, on aliphatic or aromatic sulphonic acid amides, whereby theamino groups are thereafter similarly formed in the condensationproduct.

For the production of the-capillary active agents there may further beused aromatic amino compounds following the general formulae Sucharomatic amino compounds are for instance 3 amino benzolbenzolsulphimide, 3- amino-benzol-4'-methyl-benzol sulphimide,amino-benzol-methane-sulphimide or another3-amino-benzol-alkan-sulphimide, S-amino-bexizoi-benzol-sulphimide-ii'carbonic acid, 3.3'diamino-dibenzol-sulphimide or its core substitutionproducts, such as for instance halogen-, hydroxy1-, methyl-, ethyl-,methoxy-, ethoxy-, phenoxy-, amino-substituted products and the Theseamino-diaryl-sulphimides, for instance, can be obtained by theconversion of arylas sulphochlorides, which contain in the aryl resiorNHQ'ALCO'NH'SOZ'R due a group which is convertible into an aminoNHBALSOQ H COR group; with alkylor aryl-sulphamides, and by ThefOlIOWiilg are examples of amino-aryl com, pounds of the general formulareferred to: N -(3- amino benzol sulphonyl) 5 acetamide, N (3aminoi-chloror 4-alkoxy-benzol-sulphonyl)- a'cetamide, N-(3-amino-4methyl benzol sulphonyl) -propionamide, N-(4-amino-benzol sulphonyl)-butyryl-amide, N- (3-amino-benzol-sulphonyl) -1auramide, N-(3-amino-benzol-sulphonyl) -benzamide, N- (3- ora-amino-benzoylimethane-sulphamide, N- (3-amino-4 -methyl-benzoyl)benzol-sulphamide, N (3' amino benzoyl) 3- amino-benzol-sulphamide, N3'-amino-4-methoxy-benzoyll-l-amlno benzol sulphamide, and

the like.

The amino compounds mentioned are produced in the usual way, for exampleby acting with aryl sulphonamides, or salts thereof, the aryl residue ofwhich containsa group capable of conversion into an amino sroup, onaliphatic or aromatic carboxylic'acid chlorides. .Upon completion of thereaction, the amino groups are formed from the groups that permit ofconversion into an amino group, for which latter the acylamino roups andnitro groups chiefly come into con- I sideration. The aromatic aminocompounds mentioned can further be produced by the action of aromaticcarboxylic acid chlorides, the arcivertible into an amino group, that isior instance,

of a nitroor acyl-amino group into the amino group. Also the oppositeway may be followed by converting aryl-sulphamides which comprise in thearyl residue a group convertibl into an amino group with alkyloraryL-sulpho-chlorides and by subsequently forming the amino group. Ineither case known processes are used.

According to this invention these aromatic amino compounds are actedupon by acylating or alkylating agents which comprise at least 3 C-atoms and about up to 18 C-atoms in the molecule. The action of theacylating or alkylating agents on the aromatic amino compounds takesplace according to methods which are known.

The acylating agents that chiefly come into consideration are the fattyacids and their functlonalderivatives, such as for example, fatty acidanhydrides, fatty acid esters, fatty acid halides, and the like, andiurtherorganic sulphonic acid halides. Esters of chlorated carboxylicacid, isocyanates, isothiocyanates, and chlorides of urea further comeinto consideration. The following alkylating agents may be mentioned:halogen alkyls, halogen alkylating products otalcohols, carboxylic acidand sulphonic acid amides,"'sulp uric acid or .aryl suiphonic acidesters of com-.

2 pounds with aliphaticnlly combined hydroxyl groups, and the like. Theforegoing alkyletins and acylating agents may also contain lipophiieresidues of higher molecular weight, 1. e., aliphatic hydrocarbonresidues with at least sixcarbon atoms, or cycle-aliphatic or aromatichydrocarbon residues which possess a side chain of at least threehydrocarbon atoms.

As examples of these acylatirig and aikyleting agents we mention thefollowing: propionic acid, butyric acid, capric acid, it mixture ofcoconut oil fatty acids, oleic acid, paimitic acid, mixtures of anyfatty acids, naphthenic acid, resin acids, acetyl chloride, acetic acidanhydride, stearic acid chloride, montanic acid chloride,cetyl-sulphonic acid chloride, stearyl-sulphonic acid chloride,chiorated carboxylic acid dodecyl ester, chlorated carboxylic acidhexadecyl ester, octylisocyanete, dodecyi-isothiocyanate,N-carbonyl-painiitic acid amide, N-carbonyl stearic acid amide,N-carbonyl-cetylsulphonic-acld amide, N-carbonyi stearyi-sulphonic acidamide, dodecyl-urea chloride, and the like. The following may bementioned asexamples oi allnvlating agents: propyl chloride,octylchloride, dodecyl chloride, octylchloride, dodecyl chloride,dodecyl-ohlor-methylether, hexedccyi-chlor-methyl-ether, and the like.The hydrocarbon residues oi these agents belonging to the aliphatic orcycle-aliphatic series or mixtures oi these two series, or to the fattyaromatic series, may also contain familiar hetero- 1 atoms orheteroatomic groups, or substitutes thereof, such, for example, ashalogen, hydroxyl r p and so on. as is the case, for example, withoctyl-hydroxy-acetyi chloride, or iso-octylphenoxy-acetyl chloride.

The agents referred to may act on the aromatic amino compounds accordingto usual methads .in an aqueous medium or in the presence of organicsolvents, according to the initial products used. If necessary, anelevated temperature may be applied for the reaction, and further, asfar as necessary, agents that bind water or acid. For

- example, scyletion by means or carhoxylic acids may also be carriedout in toluol solution in the presence of phosphorus trichloride orthionyl v chloride. In order to facilitate the reaction, these aminogroups may previously be converted into an isocyanate group upon whichthese fatty acids are allowed to act, whereby reaction takes place whilecarboxylic acid is split oil.

For the production of the capillary active agents from aromatic aminocompounds of the general formula. NHs.Ar.SO:.NI-LSO:.R mainly acylatingagents come into question, which may also contsin higher molecularlipophile residues, that is aliphatic or cycle-aliphatic hydrocarbonresidues of at least six hydrocarbon atoms in the molecule or aromatichydrocarbon residues having side chains oi at least three carbon atoms.

The compounds obtained by the process forming part of the presentinvention are of the general formula R'NH.Ar.X.NH.Y.R. In this formulaAr, x, Y, R denote the above mentioned substances. Accordingly, it is analiphatic or an aromatic residue. In the latter case the residue mayalso comprise an amino substitute which has been elkyleted or acylated.R denotes an alkyl residue orenscyl residue.

By ncyi residue there is understood the residue ECO-as well astheresidue 3.0.00 (from chlor csrboxylic acid esters) and R.NH.CO '(rromchlorides of urea or isocyanates) Thus, the capillary activessenta'produ ed acaccess? cording to this invention may have the generalformula Such compounds are, for instance,N-(3-lauroyiamino-benzol-sulphonyl)-benzamide, N-(3-pal-,mitoyl-amino-benzoyi) -methe.ne-su1phamide, N- (3'-capronoy1- aminobenzoyl) 3 capronoylamino benzol sulphamide, N (3propionylamino-benzol-sulphonyl) -'-benzamide, lyI-(Sbutyryl-amino-benzol-suphonyl -benzamide, N- (3-cepronoyl-amino-benzoi-sulphonyl) benzamide, N-(3-oapryloyl emino-benzolsuiphonyl) pr'opane-sulphamide,N-(3-caprinoyl-amino-benzolsulphonyl)-octane-sulphamide,li-(3-capry1oylamino-benzoyl) -3-capryloyi amino benzoi-sulphamlde,N-(3'- caprinoyi amino benzoyl) -3- caprinoyl amino benzoi sulphamide, N(3 capronyl-amino benzol sulphonyl) -benze.mide, N (3caprylyl-amino-benzol-sulphonyl propane-sulphamide, andN-(B-caprinyl-amino-benzol-sulphonyl) -octane-sulphamide.

Furthermore, the capillary active substances produced according to thisinvention may be of the general formula RCNHAnSOaNHBOzR, e s p e c i a,l l y R'.NH.Ar SOs.NH.SO2.Al.NH.R'. Such compounds are for instance3-lauroylamino-benzol-benzol-sulphimide,S-Iauroyl-amino-benzoyi-methane-sulphimide, 3.3'-dicapryloyl aminodibenzol sulphimide, 3-capronoy1- amino benzol benzol sulphimide,3-capryloylamino-benzo1-methane-sulphimide,3-caprinoyiprinoyl-amino-dibenzol-sulphimide.

The compounds obtained by the process formins part or this invention areamorphous bodies and possess surface-active properties. They also arepossessed of a considerable detergent and efrothing property, even ifthe residues that have been introduced by acylation or slkylation are ofa relatively low molecular character. Th optimum oi detergent propertyis present in such compounds in which the hydrocarbon residue Rcomprises about from 6 to 10 carbon atoms. The compounds, therefore, mayadvantageously be employed in connection with washing, cleaning,wetting, dispersing and emulsifying processes, such as are customary inthe textile and laundryindustry, fur-industry, leather-industry andother industries. The products may be used as such or also incombination with mown washing and cleaning agents or asan addition tosuch agents.

Example 1 276 parts by weight oi N-(S-amino-benzol-sulphonyl) -benzamideare dissolved in 1500 parts by weight or water with the addition of 40parts by weight of sodium hydroxide. After adding 200 parts by weight ofcrystallized sodium acetate, the solution is cooled to 2 degr. C. and amixture oi 300 parts by weight of olcic acid chloride and 300 parts byvolume or acetone are stirred in at a temperature of 2 to 5 degr. C.Stirring is kept up for half an hour at 2 degr. 0.. soc parts by weightof water are added, and the whole is treated with 20 percent sodasolution until litmus paper shows a neutral reactions Condensation iscompleted by heating the reaction mixture for one hour at 50 degr. C.The clear, thickish solution is'then the salt has dissolved, the mixtureis cooled toabout 5 degr. C. "I'heprecipitate is removed by pressure orcentrifuging and dried at 100 degr. C.

It represents an amorphous mass that dissolves in water, producing aheavy froth. The yield of the condensation product is-between 85 and 90percent of the theoretical. Its formula is Ira CuHrCO-NH Or-N-CO Example2 276 parts by weight of N-(3'-amino-benzoyl-) benzol sulphamide aredissolved inj1500 parts by weight of pyridine and the solution is cooledto. 2 degr. G. Then 240 parts by weight of lauric acid chloride dilutedwith an equal volume of acetoneto froth. The yield is similar to that ofExample 1. I

Example 3 An aqueous solution of the sodium salt of 291 parts by weightof N-(8'-amino-benzoyl)-3- amino benzene-sulphamlde oi the formula HN OSOz -NK-C OONH:

is prepared as described in Example 1.- After having added 300 parts byweight of crystalline sodium acetate, 350 parts by weight of caprylicacid chloride are gradually added at to 5 degr.

C. After neutralization with soda, the reaction is completed by heatingto 50 degr. C., as described in the foregoing Example 1, and thecondensation product is recovered in excellent yield, as theredescribed, by salting out, filtering, and drying. In spite of the factthat the alkyl residues are of comparatively low molecular weight, theproduct possesses remarkably good detergent properties. 7

A Example 4 236 parts by weight of the sodium salt of N-(3-amino-benzene-sulphonyl) -acetamide, 250 parts by weight 'of n-dodecylbromide, 30 parts by weight of magnesium oxide, 1200 parts by weight ofalcohol, and 1200 parts by weight of water are heated for six hours at150 degr. C. in an autoclave fitted with a stirrer. The reaction liquidis filtered, while Still hot, to the filtrate is added hydrochloricacid, and the bright amorphous. precipitate after cooling is removed bysuction,

filtered and dried. The product is of a waxy nature and dissolves easilyin hot dilute soda solution while frothing. 4

. Example 5 155 parts by weight of thionyl chloride are caused totrickle under stirrlngat a temperature of about 30 0. into a mixtureconsisting of 164 parts by weight of 8.3'-diamino-dibenzol-sulphimide,parts by weight of caprylic acid and 900 parts by. weight of toluol; themixture is thereupon heated for some hours at the reflux cooler toboiling condition. On ceasing development of gas the non-dissolvedreaction product is separated by suction and washed-with toluol. Theresidue is dissolved in soda solution, precipltated by means of dilutedhydrochloric acid and recrystallized from alcohol (melting point at 173C.) By treatment with soda lye the formed 3.3 dicapryloyl aminodibenzol-sulphimide is converted into the sodium salt which is solublein water yielding vigorously frothing solutions.

By replacing the caprylic acidby a mixture of fatty acids (C1-C9) havingan acid number 390, which mixture is obtained by oxidation of parafflne,there will result a product having similar properties.

Example 6 215 parts by weight of;dod'ecyl-isocyanate are caused totrickle well cooling into a solution} consisting of 326 parts byweightof 4-methyl-3- aminobenzol-benzol-sulphimide and 900 parts by weight ofpyridine; the mass is f subsequently stirred for some time at 50 C. Onremoving the pyridine by distillation the residue is worked in themanner stated in Example 1 and converted into the corresponding sodiumsalt. There will be obtained a good yield of a condensationproducthaving the formula:

agent which consists in adding an alkaline salt,

oi. an aliphatic carboxylic acid to an alkaline aqueous solution of N-(3aminobenzol-sulphonyl) benzamid'e, coolin adding a mixture oi oleic acidchloride and 'acetone with agitation and cooling, diluting with water,neutralizing with an alkaline solution, heating to condensation andprecipitating with sodium chloride.

2. A process for producing a capillary active agent which consists inadding an alkaline salt of an aliphatic carboxylic acid to an alkalineaqueous solution of N-( 3 aminobenzol-sulphonyl) benzamlde, cooling,adding a mixture of afatty acid chloride and acetone with agitationandcooling, diluting with water, neutrallzing with an alkaline solution,heating to condensation and precipitating with sodium chloride. 3. Acompound of the formula mmscmau.

